TW201629286A - Fabric and fiber product - Google Patents

Abstract

In order to provide a fabric and a fiber product, which have hygroscopicity and durability as well as flame retardancy, a hydrophilizing agent is added to a fabric containing aramid fibers.

Description

Cloth and fiber products

The present invention relates to a fabric and a fibrous product having water absorbing properties which are not only flame retardant but also durable.

In the past, since fabrics containing polyarylene fibers have excellent flame retardancy, they have been used for fire-fighting clothes or work clothes. In addition, firefighters or operators have more opportunities to perform activities in environments with higher temperatures or humidity, and there is a problem of sweating. However, the protection of firefighters or operators from flames is preferred, and the ease of use of fabrics has so far been seldom considered.

On the other hand, as a fabric for improving the comfort of sweating, it has been proposed to efficiently absorb the generated sweat (see, for example, Patent Document 1).

However, a cloth having not only flame retardancy but also water-repellent durability is rarely proposed.

[Previous Technical Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2011-94285 Newspaper

The present invention has been made in view of the above circumstances, and an object thereof is to provide a fabric and a fiber product which have not only flame retardancy but also durability and water absorbability.

As a result of intensive review in order to achieve the above-mentioned problems, the inventors of the present invention have found that by providing a hydrophilizing agent to a fabric containing polyarmine fibers, it is possible to obtain a water absorbent fabric which is not only flame retardant but also has durability. The present invention has been completed by further in-depth review.

As described above, according to the present invention, it is possible to provide "a fabric comprising a fabric comprising polyaramide fibers, which is characterized by being provided with a hydrophilizing agent."

In this case, the polyarmine fiber preferably contains 30 to 97% by weight of the meta-polyarsenamide fibers and 3 to 70% by weight of the para-polyamine fibers.

Further, the degree of crystallization of the meta-type wholly aromatic polyamide fiber is preferably in the range of 15 to 25%. Further, it is preferable that the meta-type wholly aromatic polyamine of the meta-type wholly aromatic polyamide fiber is formed in an aromatic polyamine skeleton including a repeating structural unit represented by the following formula (1). Making an aromatic diamine different from the main constituent unit of the repeating structure The fractional or aromatic dicarboxylic acid halide component is copolymerized as a third component so as to be 1 to 10 mol% based on the total amount of the repeating structural unit of the aromatic polyamine. Aromatic polyamine.

-(NH-Ar1-NH-CO-Ar1-CO)-...(1)

Here, Ar1 is a divalent aromatic group having a bonding group other than the meta coordination or the parallel axis direction.

In this case, the aromatic diamine as the third component is preferably the formula (2) or (3), or the aromatic dicarboxylic acid halide is the formulas (4) and (5).

H ₂ N-Ar2-NH ₂ (2)

H ₂ N-Ar2-Y-Ar2-NH ₂ (3)

XOC-Ar3-COX...(4)

XOC-Ar3-Y-Ar3-COX...(5)

Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, and Y is at least one atom selected from an oxygen atom, a sulfur atom, or an alkyl group. Base, X represents a halogen atom.

Further, the amount of the residual solvent of the meta-type aromatic polyamide fiber is preferably 0.1% by weight or less. Further, the fabric preferably further comprises a conductive fiber. Further, the fabric preferably further comprises a polyester fiber. Further, the polyester fiber is preferably a polyester fiber containing a flame retardant. Further, the polyarmine fiber and/or the conductive fiber and/or the polyester fiber are preferably contained in the fabric as a textile yarn. Further, the polyarmine fiber and the polyester fiber are preferably contained in the fabric as a blended yarn. In addition, the fabric preferably has a two-layer fabric structure. Further, the aforementioned hydrophilizing agent is preferably a polyethylene glycol diacrylate or a polyethylene glycol diacrylate derivative or a polyethylene terephthalate-polyethylene glycol copolymer or a water-soluble polyaminocarboxylic acid. ester. Further, the basis weight of the fabric is preferably in the range of 130 to 260 g/m ² . Further, it is preferred to carry out dyeing processing on the fabric. Further, in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, the residual flame is preferably 2.0 seconds or shorter. Further, the water absorption performance according to AATCC79 is preferably 10 seconds or less. Further, after 20 times of washing according to ISO 6339; 2012 (6N-F), the water absorption performance according to AATCC 79 is preferably 30 seconds or less.

Further, according to the present invention, there can be provided a fibrous product which is formed using the aforementioned fabric and which is selected from the group consisting of protective clothing, fire fighting clothing, fire fighting clothes, rescue clothes, overalls, police uniforms, self-defense suits, and military uniforms. Either.

According to the present invention, it is possible to obtain a fabric and a fibrous product which are not only flame retardant but also have durability and water absorbability.

Figure 1 is a diagram of the texture of the fabric used in Example 3.

Hereinafter, embodiments of the present invention will be described in detail.

First, the fabric of the present invention contains polyarylene fibers (all aromatic polyamide fibers). In the case where the polyamidamide fiber is not contained in the fabric, sufficient susceptibility cannot be obtained, which is not preferable.

The polyarsenamide fiber may be a meta-polyarsenamide fiber or a para-polyaramid fiber.

As the meta-type melamine fiber, both the original type and the dyed type can be used. A flame retardant type containing a flame retardant may also be used. Further, the less residual solvent system of the meta-polyarsenamide fibers is preferably as small as possible. Since the fiber itself has a high self-ignition property because the residual solvent is small, it is preferably 1% by weight or less (more preferably 0.3% by weight or less).

The inter-meric polyarsenic fiber is formed by an amine ring constituting a main skeleton bonded to a meta position by a guanamine bond, and more than 85 mol% of the total repeating unit of the polymer is a phenyl group. The metaphenylene isophthalamide unit is the subject. In particular, a poly(phenylisodecylamine homopolymer) is preferred. The third component obtained by copolymerization of 15 mol% or less (preferably 5 mol% or less) of the total repeating unit can be exemplified as described later. For example. Examples of the diamine component include p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, p-xylene diamine, biphenyldiamine, and 3,3. '-Dichlorobenzidine, 3,3'-dimethylbenzidine, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,5-naphthalene An aromatic diamine such as an amine. Further, examples of the other acid component include citric acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and the like. Aromatic dicarboxylic acid. Further, in the aromatic diamine and the aromatic dicarboxylic acid, one of the hydrogen atoms of the aromatic ring may be substituted with an alkyl group such as a halogen atom or a methyl group. When 20% or more of the total end of the polymer is blocked by a monovalent diamine or a monovalent carboxylic acid component such as aniline, in particular, even if it is maintained at a high temperature for a long period of time, the strength of the fiber is reduced, so that good. In the meta-type linalylamine fiber, a flame retardant or an ultraviolet absorber or other functional agent may be contained in order to maintain pigment or functional properties such as carbon black. In addition, as a commercially available product, there are Conex (registered trademark), Nomex (registered trademark), and the like.

Such a meta-type wholly aromatic polyamine can be produced by an interfacial polymerization method known in the past, and in terms of the degree of polymerization of the polymer, it is preferred to use N-A at a concentration of 0.5 g/100 ml. The intrinsic viscosity (IV) measured by the thiopyridinone solution is in the range of 1.3 to 1.9 dl/g.

The above-mentioned meta-type wholly aromatic polyamine may also contain a sulfonium alkylbenzenesulfonate. As the sulfonium alkylbenzenesulfonate, a tetrabutylphosphonium hexylbenzenesulfonate, a tributylbenzylphosphonium hexylbenzenesulfonate, a tetraphenylphosphonium dodecylbenzenesulfonate, and a dodecyl group are preferable. A compound such as tributyltetradecyl sulfonate benzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate or tributylbenzylammonium dodecylbenzenesulfonate. Among these, tetrabutylphosphonium dodecylbenzenesulfonate or tributylbenzylammonium dodecylbenzenesulfonate is easy to obtain, and has good thermal stability, and is also N-methyl-2. The solubility of pyrrolidone is also high, and thus it is particularly preferable to exemplify these.

The content ratio of the above alkyl benzene sulfonate salt is obtained in order to obtain The effect of improving the dyeability is preferably 2.5 mol% or more, preferably 3.0 to 7.0 mol%, based on the poly(isophenylene).

Further, as a method of mixing poly(phenylisodecylamine) with a sulfonium alkylbenzenesulfonate, a poly(m-phenylisodecylamine) may be mixed in a solvent to dissolve, and an alkyl group may be further added. A method in which a sulfonium sulfonate salt is dissolved in a solvent or the like can be used. The stock solution obtained in this way is formed into a fiber by a method known in the past.

The polymer used in the meta-type wholly aromatic polyamide fiber can also contain a repeating structural unit represented by the following formula (1) for the purpose of improving dyeability or fading resistance. In the aromatic polyamine skeleton, an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main constituent unit of the repeating structure is used as a third component in a repeating structural unit with respect to the aromatic polyamine. Copolymerization is carried out in a total amount of 1 to 10 mol%.

-(NH-Ar1-NH-CO-Ar1-CO)-...(1)

Here, Ar1 is a divalent aromatic group having a bonding group other than the meta coordination or the parallel axis direction.

Further, it is also possible to carry out copolymerization as the third component. Specific examples of the aromatic diamine represented by the formulas (2) and (3) include p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, acetylphenylenediamine, and amine anisidine. , benzidine, bis(aminophenyl)ether, bis(aminophenyl)anthracene, diaminobenzimidamide, diaminoazobenzene, and the like. As Specific examples of the aromatic dicarboxylic acid dichloride represented by (4) and (5) include, for example, phthalic acid chloride, 1,4-naphthalene dicarboxylic acid chloride, and 2,6-naphthalene dicarboxylic acid. Chloride, 4,4'-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis(chlorocarbonylphenyl)ether, and the like.

H ₂ N-Ar2-NH ₂ (2)

H ₂ N-Ar2-Y-Ar2-NH ₂ (3)

XOC-Ar3-COX...(4)

XOC-Ar3-Y-Ar3-COX...(5)

Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, and Y is at least one atom selected from an oxygen atom, a sulfur atom, or an alkyl group. Base, X represents a halogen atom.

In addition, the degree of crystallization of the meta-type wholly aromatic polyamide fiber is good in terms of the exhaustion of the dye, and is easier to adjust to the target color under less dye or even if the dyeing conditions are weak. Good for 5~35%. Further, it is more preferably 15 to 25% in terms of being less likely to cause the surface of the dye to be biased and the fading resistance to be high, and also to ensure practical dimensional stability.

In addition, the residual solvent amount of the meta-type wholly aromatic polyamide fiber does not impair the excellent flame retardancy of the meta-type wholly aromatic polyamide fiber and does not easily cause the surface of the dye to be biased and resistant. In terms of high discoloration, it is preferably 0.1% by weight or less.

The meta-type wholly aromatic polyamide fiber can be produced by the following method, and specifically, it can be crystallized by a method described later. The amount of the solvent or residual solvent is set to the above range.

The polymerization method of the meta-type wholly aromatic polyamine polymer is not particularly limited, and for example, Japanese Patent Publication No. Sho 35-14399, U.S. Patent No. 3,360,595, Japanese Patent Publication No. SHO 47-10863, and the like can be used. The solution polymerization method and the interfacial polymerization method described in the above.

The spinning solution is not particularly limited, and an amide-based solvent solution containing an aromatic copolymerized phthalamide polymer obtained by the above solution polymerization or interfacial polymerization may be used, or the polymer may be isolated from the above polymerization solution. And dissolved in a guanamine-based solvent.

Here, examples of the amide-based solvent to be used include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP). Dimethyl hydrazine, etc., particularly preferably N,N-dimethylacetamide.

The copolymerized aromatic polyamide polymer solution obtained as described above is stabilized by further containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and at a lower temperature, and is preferably used. The alkali metal salt and the alkaline earth metal salt are preferably 1% by weight or less (more preferably 0.1% by weight or less) based on the total weight of the polymer solution.

In the spinning/solidifying step, the spinning liquid (meta-type wholly aromatic polyamine polymer solution) obtained above is spun in a coagulating liquid and solidified.

The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. In addition, as long as it is stable for wet spinning, the number of spinning holes, the state of the arrangement, the shape of the hole, etc. of the spinning metal port are not required. Particularly, for example, a porous spinning metal port for artificial staple fibers having a number of holes of 1,000 to 30,000 and a spinning aperture of 0.05 to 0.2 mm can be used.

Further, the temperature of the spinning liquid (meta-type wholly aromatic polyamide polymer solution) when spun from the spinning metal port is preferably in the range of 20 to 90 °C.

The coagulation bath used for obtaining the fiber is substantially free of inorganic salts in the range of the bath temperature of 10 to 50 ° C, and the concentration of the guanamine-based solvent (preferably NMP) is 45 to 60% by weight. Aqueous solution. When the concentration of the guanamine-based solvent (preferably NMP) is less than 45% by weight, the skin tends to have a thick structure, and the cleaning efficiency in the washing step is lowered, and it is difficult to reduce the amount of residual fiber in the fiber. . On the other hand, when the concentration of the guanamine-based solvent (preferably NMP) exceeds 60% by weight, uniform solidification cannot be performed until reaching the inside of the fiber, so that it is difficult to reduce the amount of residual solvent of the fiber after all. Further, the immersion time of the fibers in the coagulation bath is preferably in the range of 0.1 to 30 seconds.

Then, in a plastic extension bath having a concentration of 45 to 60% by weight of a guanamine-based solvent (preferably NMP), and a bath temperature of 10 to 50 ° C, 3 to 4 times. The extension ratio is extended. After the extension, the concentration of NMP at 10 to 30 ° C is 20 to 40% by weight, and then thoroughly washed by a warm water bath at 50 to 70 ° C.

The washed fiber is subjected to dry heat treatment at a temperature of 270 to 290 ° C to obtain a position-type wholly aromatic polyaramide fiber which satisfies the above-mentioned degree of crystallization and the amount of residual solvent.

Further, the para-polyaramid fiber is a fiber composed of a polyamine having an aromatic ring in the main chain. The copolymerization of poly-p-phenylene terephthalamide (PPTA) and a copolymerization type may be carried out on phenyl-3,4'-oxydiphenylene p-nonylamine (PPODPA). In addition, as a commercial product, there are Technora (registered trademark), Kevlar (registered trademark), and Towaron (registered trademark).

Specifically, when the polyarsenamide fiber contains 30 to 97% by weight of the meta-polyalkylamine fiber and 3 to 70% by weight of the para-polyamine fiber, the shrinkage of the cloth during burning will occur. It is preferable that it becomes small and it becomes difficult to drill a cloth.

The fabric of the present invention may be composed only of the polyarmine fibers as described above, and may contain fibers (other fibers) other than the polyarylene fibers.

For example, when the conductive fiber is contained in the fabric, it is preferable to suppress the flame caused by the static electricity generation by the synergistic effect with the hydrophilizing agent imparted to the fabric.

As such a conductive fiber, a fiber containing at least one of carbon black, conductive titanium oxide, conductive whiskers, and carbon nanotubes as a conductor of a conductive portion of the conductive fiber is preferable.

The form of the conductive fiber may be a structure in which the entire fiber is composed of a conductive portion, or the non-conductive portion and the conductive portion may have a cross-sectional shape such as a core sheath, a sandwich, or an eccentric core. The resin forming the conductive portion and the non-conductive portion is not particularly limited as long as it has fiber formability. Specifically, on the nylon tree Examples of the fat include those of nylon 6, nylon 11, nylon 12, and nylon 66. Further, as the polyester resin, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane p-citric acid may be mentioned. The ester and the copolymer or the acid component (p-citric acid) are partially replaced with isophthalic acid.

As a commercially available conductive fiber, "Metalian" (product name) manufactured by Teijin Co., Ltd., "Megana" (product name) manufactured by Unitika Fibers Co., Ltd., "Luana" (trade name) manufactured by Toray Industries, and "Kuracarbo" manufactured by Kuraray Co., Ltd. (trade name), etc.

Further, fibers such as polyester fiber, nylon fiber, acrylic fiber, acrylate fiber, flame retardant fiber, and flame retardant vinylon fiber may be contained in the fabric. Specifically, when the polyester fiber is contained in the fabric, the water absorbing property is further improved, which is preferable.

The aforementioned polyester fiber is a fiber containing polyester as a component. The polyester is based on phthalic acid as a main dicarboxylic acid component and at least one diol, preferably at least one alkylene glycol selected from the group consisting of ethylene glycol, trimethylene glycol, tetramethylene glycol and the like. The main diol component of the polyester. In the above polyester, it may be denatured by copolymerization and/or blending of the third component as needed. As such a polyester, polyethylene terephthalate formed by using a monomer obtained by recovering or chemically recovering a material or a raw material (that is, a substance derived from a living material) as a raw material can be used. Further, a polyester obtained by using a catalyst containing a specific phosphorus compound and a titanium compound as described in JP-A-2004-270097 or JP-A-2004-211268 may be used.

Further, the polyester may optionally contain any additives such as a catalyst, a coloring preventive agent, a heat resistant agent, a flame retardant, an antioxidant, inorganic fine particles, and the like. Specifically, when a flame retardant is imparted to the polyester polymer or the surface of the polyester fiber, the flame retardancy of the fabric is improved, which is preferable.

In the polyester fiber, the single fiber fineness is preferably 5.0 dtex or less (more preferably 0.0001 to 1.5 dtex) in terms of increasing the surface area of the fiber to obtain excellent sweat absorption and the like.

In the polyester fiber, the cross-sectional shape (cross-sectional shape) of the single fiber is preferably a foreign shape (a shape other than a circular shape). As such a profiled cross-sectional shape, a flat cross section or a W-shape or a cross or a hollow (for example, a circular hollow, a triangular hollow, a four-corner hollow, or the like) or a triangle is preferable. Further, it may be a flat cross section having a constricted neck as described in Japanese Laid-Open Patent Publication No. 2004-52191, and has a hollow core portion as disclosed in Japanese Laid-Open Patent Publication No. 2012-97380. The section of the radial fin section. By having an irregular cross-sectional shape of the organic fiber, voids can be generated between the fibers, and excellent water absorbability can be obtained due to the capillary phenomenon. In addition, the water absorbed by the water absorbing effect also has a synergistic effect of further improving the flame retardancy. Among the cross-sectional shapes described above, the W-type system is particularly preferable because a small amount of fibers can easily form voids between the fibers.

The polyester fiber may be a composite fiber in which two components are arranged in parallel or in an eccentric core sheath type. Since such a conjugate fiber generally has a fine crimp which exhibits a potential crimp, it has not only stretchability but also superior water absorbability due to capillary action.

In this case, the two components constituting the composite fiber are preferably selected from the group consisting of a combination of polytrimethylene terephthalate and trimethylene terephthalate, a combination of polytrimethylene terephthalate and polyethylene terephthalate. Any combination of a combination of polyethylene terephthalate and polyethylene terephthalate.

In the fabric of the present invention, the fiber form of the polyarmine fiber or other fibers constituting the fabric is not particularly limited, and may be a short fiber (woven yarn) or a long fiber (multifilament). Specifically, in terms of sufficiently maintaining the durability of the hydrophilizing agent, the textile yarn is preferred.

At this time, the polyarylene fiber or other fibers may be blended at the same time, or may be used individually and interwoven and interwoven. Among these, when the polyarmine fiber and the polyester fiber are blended and contained in the fabric as a blended yarn, not only excellent flame retardancy but also the hydrophilizing agent can sufficiently maintain the washing durability. It is better.

Further, when the textile yarn is spiral, it is preferable to impart stretchability to the fabric. Such a helically woven textile yarn can be obtained by, for example, the following method.

That is, first, a textile yarn containing polyarmine fibers is prepared. At this time, conductive yarn or other fibrous raw cotton may be mixed in the polyarsenamide fiber. The fineness (number of counts) of the textile yarn is preferably from 20 to 60 counts in terms of yarn count (Ecc) in terms of yarn breakage resistance or strength. The number of single yarns is preferably 60 or more, and the raw yarn single yarn fineness is preferably 3.0 dtex or less (more preferably 0.001 to 3.0 dtex). The coefficient of the weft of the textile yarn (the lower jaw coefficient) is preferably in the range of 3.6 to 4.2 (more preferably 3.8 to 4.0). The larger the 捻 coefficient, the more the fluff is condensed, and the pilling resistance of the fabric becomes good. Ok, on the other hand, the textile yarn becomes straight, and there is a fear that the elongation of the fabric is lowered and the fabric of the fabric is reduced and the fabric is hardened. In addition, the 捻 coefficient is expressed by the following formula.

捻 coefficient = number of turns (time / 2.54cm) ^/ cotton count of textile yarn (Ecc) ^1/2

The textile method of the textile yarn can be a general textile method such as ring spinning, MTS, MJS, MVS, etc., such as innovative textile or ring spinning. The twisting direction is either the Z direction or the S direction.

Next, after the skein type (vacuum vapor setting) is required for the woven yarn, two or more (preferably 2 to 4, particularly preferably 2) woven yarns are combined and combined. twist. As the crepe machine used in the merging, a skeining machine such as an up-and-down twisting machine, a wire wrapping machine, an Italian crepe machine, and a double twisting machine can be exemplified.

At this time, the twisting direction of the merge (top) is the tracking direction. For example, in the case where the twisting direction of the textile yarn is Z-twisted, twisting is performed in the Z direction in the same direction. Further, the number of turns is preferably 2,000 times/m or more, more preferably 2,100 to 3,000 times/m, and particularly preferably 2,300 to 2,800 times/m. When the number of turns is less than 2,000 times/m, there is a doubt that the shape of the textile yarn does not become a spiral after the stagnation type and the smashing.

Next, the twisted yarn of this type of twisted yarn was subjected to a stagnation type (high pressure vacuum vapor setting similar to the conventional polyamidamide double yarn stagnation type). In the case where it is necessary to give a strong stagnation type, the number of stagnation types can be increased, the stagnation setting temperature or the sizing time can be changed. For example, the setting temperature can be 115~125°C, and the setting time can be 20~40 minutes. The number of times can be 1~3 times, and the higher the setting temperature, and the longer the setting time, the better the setting. It is possible to further improve the setting by increasing the number of stop-types, lengthening the processing time, and increasing the temperature. However, it is preferable to lengthen the production management (operation management safety, quality management, etc.) or production and processing costs. Processing time. Further, it is preferred that the higher the degree of vacuum, the better the quality.

Next, the twisted yarn of the fixed type is untwisted (the direction of twisting in the opposite direction to the twisting direction of the twist), and heat setting is performed as needed. In this case, the number of twists is preferably in the range of 70 to 90% of the number of twists. By performing the untwisting of the number of turns in this range, a textile yarn processed into a spiral shape having stretchability can be obtained. In the textile yarn which is processed into a spiral shape, the number of turns is preferably in the range of 200 to 860 times/m in terms of obtaining excellent stretchability.

The structure of the fabric is not particularly limited, and examples thereof include plain weave, twill weave, and double weave. Among these, if the structure of the fabric has a double-layered woven structure having a two-layer structure, the water absorbing property is further improved, which is preferable. In this case, the fibers constituting the double-layered yarn are not particularly limited, and it is preferable that the yarn mainly exposed to the layer on the muscle side is composed of 10% by weight or more of polyester fibers, and mainly faces the outer gas side layer. The exposed yarn is composed of polyester fibers in the range of 0 to 10% by weight. By blending a polyester fiber having a large water absorption property in the yarn which is mainly exposed to the muscle side, the water absorption property is improved, and the polyester fiber content is reduced in the yarn which is mainly exposed to the outer gas side layer, It can maintain the overall flame retardant performance of the fabric.

In the fabric of the present invention, not only flame retardancy but also water-repellency with durability is imparted by imparting a hydrophilizing agent.

Here, as the hydrophilizing agent, a derivative of polyethylene glycol diacrylate or polyethylene glycol diacrylate or a polyethylene terephthalate-polyethylene glycol copolymer or a water-soluble polyamine group is preferred. Formate or polyethylene glycol-amine polyoxyl copolymer.

The adhesion amount of the hydrophilizing agent to the fabric is preferably from 0.1 to 2.0% by weight (more preferably from 0.1 to 0.7% by weight) based on the weight of the comparative fabric. Further, the amount of adhesion of the hydrophilizing agent can be calculated by the following formula.

The amount of adhesion of the hydrophilizing agent (%) = ((the weight of the fabric after the hydrophilizing agent is attached) - (the weight of the fabric before the hydrophilizing agent is attached)) / (the weight of the fabric before the hydrophilizing agent is attached) ×100

However, the weight of the fabric after the hydrophilizing agent is attached is the weight after drying.

The method of applying the hydrophilizing agent to the fabric may, for example, be a method of performing a padding treatment, a method of treating the same with a dyeing liquid during dyeing, and the like.

Preferably, the fabric is subjected to dyeing processing. Further, other various processes such as a water repellent, a heat storage agent, an ultraviolet shielding or a power generating agent, an antibacterial agent, a deodorizing agent, an insect repellent, an anti-mosquito agent, a light storing agent, and a retroreflective agent may be additionally applied.

In the fabric thus obtained, the basis weight is preferably from 130 to 260 g/m ² (more preferably from 140 to 220 g/m ² ).

Since such a fabric contains a polyamidamide fiber as described above and is provided with a hydrophilizing agent, it has not only flame retardancy but also water absorbability which is durable.

Here, in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, the afterflame is preferably 2.0 seconds or less. Further, the water absorbing performance of the flame-retardant fabric is preferably such that the water absorption performance according to AATCC79 is 10 seconds or less in the initial stage (more preferably 0.1 to 8 seconds in the initial stage). Further, the water absorption performance according to AATCC79 is preferably 30 seconds or less (more preferably 1 to 20 seconds) after 20 times of washing according to ISO 6339; 2012 (6N-F).

The fiber product of the present invention is formed using the aforementioned fabric and is selected from the group consisting of protective clothing, fire-fighting clothing, fire-fighting sportswear, rescue clothes, overalls, police uniforms, self-defense suits, and military uniforms.

Since the above-mentioned fabric is used for such a fiber product, it has not only flame retardancy but also water absorbency with durability.

[Examples]

Next, the examples and comparative examples of the present invention will be described in detail, but the present invention is not limited thereto. Further, each physical property in the examples was measured by the following method.

(1) The amount of residual solvent

About 8.0 g of fibrils was taken, and it was dried at 105 ° C for 120 minutes, and then allowed to cool in a desiccator, and the fiber weight (M1) was weighed. Subsequently, for this fiber, reflux extraction was carried out in methanol using a Soxhlet extractor for 1.5 hours, and extraction of a guanamine-based solvent contained in the fiber was carried out. Take out the extracted fiber and let it After drying in a vacuum at 150 ° C for 60 minutes, it was allowed to cool in a desiccator, and the fiber weight (M2) was weighed. The amount of the solvent remaining in the fiber (the weight of the amide-based solvent) was calculated by the following formula using the obtained M1 and M2.

Residual solvent amount (%) = [(M1-M2)/M1] × 100

Using the obtained fibrils, crimping and cutting were performed to obtain staple fibers (raw cotton) having a length of 51 mm.

(2) Degree of crystallization

Using a X-ray diffraction measuring apparatus (RINT TTRIII, manufactured by Rigaku Co., Ltd.), the fibrils were bundled into a fiber bundle having a diameter of about 1 mm, and mounted on a fiber sample stage to measure a diffraction curve. The measurement conditions were Cu-Kα ray source (50 kV, 300 mA), scanning angle range of 10 to 35°, continuous measurement of 0.1° width measurement, and 1°/min scanning. A full scattering curve is obtained by correcting the air scattering and non-interference scattering by a linear approximation from the measured diffraction curve. Next, the amorphous scattering curve is subtracted from the full scattering curve to obtain a crystal scattering curve. The degree of crystallization is determined by the following equation from the area intensity (crystal scattering intensity) of the crystal scattering curve and the area intensity (total scattering intensity) of the total scattering curve.

Crystallization degree (%) = [crystal scattering intensity / total scattering intensity] × 100

[Example 1]

A meta-type wholly aromatic polyamide fiber (MA) composed of Conex (registered trademark), a para-type wholly aromatic polyamide fiber (PA) composed of Towaron (registered trademark), manufactured by Solcia Each of the staple fibers (51 mm long) of conductive nylon fiber (NY) consisting of "NO SHOCK (registered trademark)" is blended at a weight ratio of MA/PA/NY=93/5/2. 40 yarns/double yarns of textile yarns, weaving flat fabrics with a weaving density of 56/25.4mm, weft 48/25.4mm, and after singeing and refining under the normal processing conditions, the dyeing treatment method is used to impart A hydrophilizing agent of polyethylene terephthalate-polyethylene glycol copolymer was then heat-set at 180 ° C to obtain a flat fabric having a basis weight of 150 g/m ² and a hydrophilizing agent adhesion amount of 0.2 to 0.5% by weight.

In the obtained fabric, the water absorption performance according to AATCC79 was 2.0 seconds at the initial stage, and 25 seconds after washing 20 times according to ISO 6339; 2012 (6N-F), the fabric had excellent water absorbency. In addition, in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, the residual flame is 2.0 seconds or less, and there is no problem. After using this kind of fabric sewing work and wearing it, it absorbs sweat when sweating and has excellent comfort.

[Example 2]

In addition to the meta-type wholly aromatic polyamide fiber (MA), para-type wholly aromatic polyamide fiber (PA), conductive nylon fiber (NY), flame retardant polyester fiber (PE) The short fibers (having a fiber length of 51 mm) were produced in the same manner as in Example 1 except that 40 yarn counts/double yarns were obtained by blending a weight ratio of MA/PA/NY/PE=73/5/2/20. Implementation.

In the obtained fabric, the water absorption performance according to AATCC79 is 0.9 seconds at the initial stage, and 11 seconds after washing 20 times according to ISO6339; 2012 (6N-F), the fabric has excellent water absorption. Sex. In addition, in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, the residual flame is 2.0 seconds or less, and there is no problem. After using this kind of fabric sewing work and wearing it, it absorbs sweat when sweating and has excellent comfort.

[Example 3]

The same procedure as in Example 2 was carried out except that in the second embodiment, the double-layered fabric was woven according to the woven texture diagram shown in Fig. 1 at a weaving density of 56 pieces / 25.4 mm and a latitude of 60 pieces / 25.4 mm.

Among the obtained fabrics, the water absorption performance according to AATCC79 was 0.6 seconds at the initial stage, and 9.0 seconds after washing 20 times according to ISO 6339; 2012 (6N-F), and the fabric had excellent water absorbability. In addition, in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, the residual flame is 2.0 seconds or less, and there is no problem. After using this kind of fabric sewing work, it absorbs sweat when sweating, and the work clothes and the skin do not adhere to each other, and have excellent comfort.

[Comparative Example 1]

Except that the hydrophilizing agent was not provided in Example 1, the same procedure as in Example 1 was carried out. The obtained fabric had an initial water absorption performance of 58 seconds according to AATCC 79 and 48.0 seconds after washing 20 times according to ISO 6339; 2012 (6N-F), and the fabric did not have water absorption. In addition, in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, the residual flame is 2.0 seconds or less, and there is no problem. After using this kind of fabric sewing work and wearing it, it does not absorb sweat when sweating, and it is not comfortable.

[Example 4]

The meta-type wholly aromatic polyamide fiber (MA), the para-type wholly aromatic polyamide fiber (PA), the polyester fiber (PE) having a cross-sectional shape of W, and the conductive nylon fiber (NY) Each of the staple fibers (having a fiber length of 51 mm) is made of 40 yarns/double yarns of a blend of MA/PA/PE/NY=78/5/15/2 in weight ratio. 56 /25.4mm, weft 48/25.4mm woven flat fabrics, after singeing and refining under normal processing conditions, processing with polyethylene terephthalate-polyethylene glycol copolymer by padding treatment The sweat-absorbent agent was then heat-set at 180 ° C to obtain a flat fabric having a basis weight of 150 g/m ² .

In the obtained fabric, the water absorption performance according to AATCC79 was 0.5 second at the initial stage, and 8.0 seconds after washing 20 times according to ISO 6339; 2012 (6N-F), and the fabric had excellent water absorbability. In addition, in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, the residual flame is 2.0 seconds or less, and there is no problem. After using this kind of fabric sewing work and wearing it, it absorbs sweat when sweating and has excellent comfort.

[Example 5]

In addition to meta-type wholly aromatic polyamide fiber (MA), para-type wholly aromatic polyamide fiber (PA), cross-sectional shape W-type flame retardant polyester fiber (NPE), conductive nylon fiber (NY) made of staple fiber (with a fiber length of 51mm) made of MA/PA/NPE/NY=78/ A textile yarn of a ratio of 5/15/2 in a weight ratio of 40 yarns/double yarn was used in the same manner as in Example 4.

In addition, in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, the residual flame is 2.0 seconds or less, and there is no problem. In addition, the water absorption performance according to AATCC79 is 1.1 seconds at the initial stage, and 13 seconds after washing 20 times according to ISO6339; 2012 (6N-F), which has excellent water absorption and is used after sewing work. It absorbs sweat when sweating and has excellent comfort.

[Example 6]

In addition to the meta-type wholly aromatic polyamide fiber (MA), the para-type wholly aromatic polyamide fiber (PA), the cross-sectional shape of the polyester fiber (PE), conductive nylon fiber (NY Each of the staple fibers (having a fiber length of 51 mm) is made of 40 yarns/double yarns of a textile yarn blended at a weight ratio of MA/PA/PE/NY=78/5/15/2, and is implemented. Example 4 was carried out in the same manner.

The woven fabric obtained has a residual flame of 2.0 seconds or less in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, and has no problem. In addition, the water absorption performance according to AATCC79 is 1.2 seconds at the initial stage, 12 seconds after washing 20 times according to ISO6339; 2012 (6N-F), and has excellent water absorption, and after sewing and working, It absorbs sweat when sweating and has excellent comfort.

[Example 7]

Except for the artificial staple fibers (the fiber length is 51 mm) of the meta-type wholly aromatic polyamide fiber (MA), the para-type wholly aromatic polyamide fiber (PA), and the conductive nylon fiber (NY). A yarn obtained by mixing 40 yarns/double yarns of a textile yarn blended at a weight ratio of MA/PA/PE/NY=93/5/2 is used as a warp yarn, and on the other hand, the textile yarn 40 is counted/double Yarn, and composite fiber composed of polyethylene terephthalate/trimethylene terephthalate (total fineness 84dtex/24 filament) are combined and used as weft yarn, with a weaving density of 56/25.4mm, weft The same procedure as in Example 4 was carried out except for 43 /25.4 mm woven flat fabrics.

The woven fabric obtained has a residual flame of 2.0 seconds or less in the flammability measurement prescribed by the JIS L1091-1992 A-4 method, and has no problem. In addition, the water absorption performance according to AATCC79 is 1.0 second at the initial stage, 14 seconds after washing 20 times according to ISO6339; 2012 (6N-F), and has excellent water absorption, and after sewing and working, It absorbs sweat when sweating and has excellent comfort. Further, it has further stretchability in the lateral direction and is easy to move.

[Example 8]

The meta-type wholly aromatic polyaramide fiber was produced in the following manner.

20.0 parts by weight of poly(isophenylene isophthalamide) powder having an intrinsic viscosity (IV) of 1.9, which was produced by an interfacial polymerization method based on the method described in Japanese Patent Publication No. Sho 47-10863, was suspended in cooling. The slurry was in the form of a slurry of 80.0 parts by weight of N-methyl-2-pyrrolidone (NMP) at -10 °C. Then, the suspension is warmed to 60 ° C and allowed to Dissolved to obtain a clear polymer solution. The comparative polymer was made up to 3.0% by weight of 2-[2H-benzotriazol-2-yl]-4-6-bis(1-methyl-1-phenylethyl)phenol powder in the polymer solution. (Soluble to water: 0.01 mg/L), the mixture was dissolved, and subjected to vacuum decompression to obtain a spinning solution (spinning stock solution).

[spinning/coagulation step]

The spinning stock solution was spun by a spinning metal opening having a hole diameter of 0.07 mm and a number of holes of 500 to a coagulation bath having a bath temperature of 30 °C. The composition of the coagulating liquid was water/NMP = 45/55 (parts by weight), and spun in a coagulating liquid at a yarn speed of 7 m/min.

[plastic extension bath extension step]

Then, in a plastic extension bath having a composition of water/NMP = 45/55 at a temperature of 40 ° C, the stretching was performed at a stretching ratio of 3.7 times.

[washing step]

After extension, it is washed with water at 20 ° C/NMP=70/30 (dilution length 1.8 m), then washed with a water bath (immersion length 3.6 m) at 20 ° C, and further passed through a warm water bath at 60 ° C (dipping length 5.4) m) and fully perform the washing.

[dry heat treatment step]

The washed fiber was subjected to dry heat treatment using a hot roll having a surface temperature of 280 ° C to obtain a meta-type wholly aromatic polyaramide fiber.

[physical properties of fibrils]

The physical properties of the meta-type wholly aromatic polyaramide fibers were 1.7 dtex, the residual solvent amount was 0.08% by weight, and the degree of crystallization was 19%. other The fiber raw cotton is the following.

Polyester fiber; polyethylene terephthalate fiber manufactured by Teijin

Flame-retardant fiber; Lenzing FR (registered trademark) manufactured by Lenzing

Counter-type polyarylamine fiber; "Towaron (registered trademark)" by Teijin Aramid

Conductive Yarn (Nylon); "NO SHOCK (registered trademark)" manufactured by Solcia Co., Ltd. (Nylon conductive yarn mixed into conductive carbon particles)

Next, a meta-type wholly aromatic polyarylene fiber (MA) (length 51 mm), a para-type wholly aromatic polyamine (PA) (length 50 mm), a polyester fiber (length 38 mm) (PE), Each of the staple fibers of the flame-retardant enamel (Ry) (length 51 mm) is made of 40 yarns/double yarns of a textile yarn blended at a weight ratio of MA/PA/PE/RY=55/5/15/25. Weaving was carried out at a weaving density of 67/25.4 mm and a weft 56/25.4 mm to obtain a twill fabric having a basis weight of 170 g/m ² . After the dyeing and finishing by the usual method, the following sweat absorbing processing was carried out.

[clothing sweat absorption]

The test cloth was immersed in a sweat-absorbent processing agent polyethylene glycol-amine polyfluorene oxide copolymer (50 g/L), pressed and dried, and then subjected to dry heat setting at a temperature of 180 ° C for 2 minutes.

In the woven fabric obtained by the method of JIS L1091-1992 A-4, the residual flame was 2.0 seconds or less, and there was no problem. Further, the water absorption performance according to AATCC79 was 0.9 seconds at the initial stage, and 9.0 seconds after washing 20 times in accordance with ISO 6339; 2012 (6N-F). After using this kind of fabric sewing work, it absorbs sweat when sweating, and the work clothes and the skin do not adhere to each other, and have excellent comfort.

[Industrial Applicability]

According to the present invention, it is possible to provide a fabric and a fibrous product which are not only flame retardant but also have water-repellent properties with durability, and are industrially valuable.

Claims (21)

A fabric comprising a fabric of polyaramide fibers, which is characterized by being provided with a hydrophilizing agent. The fabric of claim 1, wherein the polyarmine fiber comprises 30 to 97% by weight of the meta-polyamine fibers and 3 to 70% by weight of the para-polyamine fibers. The fabric of claim 2, wherein the meta-type wholly aromatic polyamide fiber has a degree of crystallization of 15 to 25%. The fabric of claim 2, wherein the meta-type wholly aromatic polyamine of the meta-type wholly aromatic polyamide fiber is formed in an aromatic poly group comprising a repeating structural unit represented by the following formula (1) In the guanamine skeleton, an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main constituent unit of the repeating structure is used as the third component in terms of the total amount of the repeating structural unit of the aromatic polyamine. Said to be 1 to 10 mol% of the copolymerization to form a meta-type wholly aromatic polyamine; - (NH-Ar1-NH-CO-Ar1-CO)-... (1) here, Ar1 is a divalent aromatic group having a bonding group other than the meta coordination or the parallel axis direction. The fabric of claim 4, wherein the aromatic diamine as the third component is a formula (2) or (3), or the aromatic dicarboxylic acid halide is a formula (4), (5); H ₂ N- Ar2-NH ₂ Formula (2) H ₂ N-Ar2-Y-Ar2-NH ₂ Formula (3) XOC-Ar3-COX... Formula (4) XOC-Ar3-Y-Ar3- COX (5) Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, and Y is selected from an oxygen atom, a sulfur atom, and an alkylene group. At least one atom or functional group of the group, and X represents a halogen atom. The fabric of claim 2, wherein the amount of the residual solvent of the meta-type aromatic polyamide fiber is 0.1% by weight or less. The fabric of claim 1, wherein the fabric further comprises conductive fibers. The fabric of claim 1, wherein the fabric further comprises polyester fibers. The fabric of claim 8, wherein the polyester fiber is a polyester fiber containing a flame retardant. The fabric of claim 8, wherein the polyester fiber has a profiled cross-sectional shape. The fabric of claim 8, wherein in the polyester fiber, the cross-sectional shape of the single fiber is flat or W-shaped or cross or hollow or triangular. The fabric of claim 8, wherein the polyarmine fiber and/or the conductive fiber and/or the polyester fiber are contained in a fabric as a textile yarn. The fabric of claim 8, wherein the polyarmine fiber and the polyester fiber are contained in a fabric as a blended yarn. The fabric of claim 1, wherein the fabric has a double layer of fabric. The fabric of claim 1, wherein the aforementioned hydrophilizing agent is polyethylene Derivatives of diol diacrylate or polyethylene glycol diacrylate or polyethylene terephthalate-polyethylene glycol copolymer or water-soluble polyurethane or polyethylene glycol-amine polyfluorene Oxygen copolymer. The fabric of claim 1, wherein the fabric has a basis weight of 130 to 260 g/m ² . The fabric of claim 1 is characterized in that the fabric is subjected to dyeing processing. In the flammability measurement specified in the JIS L1091-1992 A-4 method, the residual flame is 2.0 seconds or less. The fabric of claim 1 wherein the water absorption performance according to AATCC 79 is 10 seconds or less. In the case of claim 1, the water absorption performance according to AATCC79 is 30 seconds or less after washing 20 times according to ISO6339; 2012 (6N-F). A fibrous product formed using the fabric of claim 1 and selected from the group consisting of protective clothing, fire fighting clothing, fire fighting clothing, rescue clothing, overalls, police uniforms, self-defense clothing, and military uniforms.